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One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch−Buttenberg−Wiechell Rearrangement

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Thanh Luu,^† Yasuhiro Morisaki,^‡ Nina Cunningham,^† and Rik R. Tykwinski*^†

Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada, and Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Nishikyo-ku, Kyoto 615-8510, Japan

J. Org. Chem., 2007, 72 (25), pp 9622–9629

DOI: 10.1021/jo701810g

Publication Date (Web): November 14, 2007

Section:

General Organic Chemistry

Abstract

A divergent, one-pot synthesis of functionalized polyynes has been developed. Beginning with the appropriately substituted dibromoolefinic precursor, a carbenoid Fritsch−Buttenberg−Wiechell (FBW) rearrangement is used to generate the lithium acetylide of a conjugated polyyne framework, and subsequent trapping with carbon-based electrophiles provides for in situ formation of a wide range of di- and triynes. The lithium acetylide formed from the FBW reaction can also undergo transmetalation to provide the corresponding zinc, copper, tin, or platinum acetylides, leading to the divergent formation of symmetrical and unsymmetrical conjugated acetylenes, as well as ynones.

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